Alkylation process



Patented Feb. 15, 1944 ALKYLATION PROCESS Arthur R. Goldsby, Beacon, N. Y., assignor, by mesne assignments, to The Texas Company, New York, N. Y., a corporation of Delaware Application June 7, 1939, Serial No. 277,796 2z Claims. (Ci. 26o-683.4)

This invention relates to the alkylation of olen hydrocarbons with paraln hydrocarbons in the presence of an alkylatlon catalyst such as concentrated sulphuric acid. It has particularaapplication to the manufacture of high anti-knock gasoline hydrocarbons suitable for use in the production of motor fuel.

Broadly, the invention contemplates a process for the alkylation of hydrocarbons wherein olefin and parailin hydrocarbons are subjected to contact with a liquid alkylation catalyst in a reaction zone. A circulating stream of isoparaiiin hydrocarbons and liquid alkylation catalyst is established and maintained in a closed. circuit by continuously drawing off a portion of the liquid mixture from the reaction zone and subsequently returning it thereto. The fresh hydrocarbon feed containing olefin hydrocarbons is continuously injected, in the gas phase, in the circulating stream prior toits return to the reaction zone. v The products of reaction are withdrawn from the zone of reaction, and unreacted hydrocarbons may be recycled.

In pending application Serial No. 203,238, :led April 21, 1938, now Patent No. 2,211,747, a process of alkylation has been described in which olen hydrocarbons are alkylated with isoparain hydrocarbons in the presence of a catalyst such as concentrated sulphuric acid. As there disclosed, a hydrocarbon mixture containing paraiiin 'and olefin hydrocarbons is brought into contact with the catalyst in one or more reaction vessels.` The reaction mixture is drawn o from the alkylation vessel to a separating vessel in which the products of reaction are separated from the used acid. A portion of the mixture of hydrocarbons and acid passing to the separating vessel is continuously recycled to the initial reaction vessel and the fresh hydrocarbon feed containing olefin hydrocarbons is injected into avoidanceof polymerization of the olefin hydrocarbons upon coming into contact with the catalyst. Moreover', the method of this invention permits .introduction of the fresh hydrocarbon feed while in gaseous form. This may be of considerable advantage, inasmuch as the fresh hydrocarbon feed is usually composed largely of normally 'gaseous hydrocarbons.

The invention is'particularly applicable to the alkylation of -oleiin hydrocarbons with paraffin hydrocarbons to produce motor fuels. been found especially successful in the alkylation of isoparailins with oleiins; for example, the

'alkylation of isobutane with'gaseous or liquid oleiins having a boiling point not greatly in exell) cess of the gasoline boiling range. It is within the scope ofy the invention, however, to alkylate any isoparailin hydrocarbon, gaseous or liquid, with olens, gaseous or liquid, in the presencev ofa uid catalyst which may be recycled in' the system.

Any fluid catalyst eiective as an alkylation catalyst may be used. For this purpose concentrated sulphuric acid, containing around to HzSOr. has been found to be effective. As an 'example of another catalyst mention may be made of a boron trifluoride-water complex having the formula BF3.nI-I z0, where n has" a value ranging from about 1 to 1.5.

In order to describe the invention more fully reference will nowbe made to the accompanying drawing comprising 'a now diagram illustrating one method of practicing the process of the invention.

Referring to the drawing, the hydrocarbon feed is conducted lfrom a source not shown through a pipe l. This hydrocarbon feed comprises, for example, a mixture of olen and paraffin hydrocarbons, such as the vapor fraction removed overhead when stabilizing a cracked naphtha produced inl the,commercial cracking of mineral ol for production of gasoline hydrocarbons. Such a fraction may comprise essentially Cr hydrocarbons or a. mixture of C3 and C4 hydrocarbons with or without lighter hydrocarbons. It includes a substantial proportion of oleiins, such as Ca and Cr olens, as well as C3 and C4 paraiiins, such as propane, normal butane and isobutane, and' may include C5 hyactor` il is of such size and capacity as to afford sufficient time for the reaction to proceed to the It has' recycled is'obutane through desired extent. The reaction mixture overows through a pipe 5 to a settler B. The reactor may be equipped with a valved gas release pipe 1 for discharge of unabsorbed gases and for control of pressure within the reactor.

A substantial portion of the mixture overflowing from the reactor 4 is passed through a pipe 8 communicating with the suction side of a circulating and agitating pump 9, such as a centrifugal pump. which forces the liquid mixture, in the form of a thoroughly dispersed emulsion, through the cooling 'coil 2. The discharge of the circulating stream into the reactor provides agitation of the mixture therein, and this may be supplemented therein by additional internal stirrers or agitators.

That portion of the overiiow mixture passing to the settler E undergoes settling and stratication therein so that catalyst liquid settles to the I lower portion thereof. 'I'he hydrocarbons separate into an upper layer which is substantially free from acid and comprise products of reaction as well as unre'acted hydrocarbons., This upper layer overflows through a pipe lli to a neutralizing vessel Il. In`the vessel Il the mixture is subjected to contact with an alkali such as caustic soda, introduced through a pipe I2. The neutralized products overflow to a settler Il', where the alkali-sludge settles to the bottom of the vessel Il' and is withdrawn therefrom, provision being made for recirculating a portion of it by a circulating pump i3.

The neutralized product passes through a pipe Id to a, fractionator |5. A vapor fraction comprising isobutane, normal butane and lighter hydrocarbons is removed through pipe I 6 leading to a fractionator Il. In the fractionator I1 isobutane and lighter constituents are removed as a vapor fraction through a pipe I8 leading to a condenser I9. Condensate and mixed gas pass to a small fractionator 20, where any propane and lighter gases are separated from the condensed isobutane, the gases passing o overhead through pipe 2i. The condensed isobutane is drawn off from the bottom of the fractionator through a pipe 22 communicating with pipe 23 leading to the suction side of the previously mentioned circulating pump 9.

The liquid fraction formed in the bottom of the fractionator i1 comprises normal butane, which is drawn off through a pipe 24. A liquid fraction formed in the bottom of the fractionator l5 is drawn o through a pipe 25 and conducted to a fractionator 26. Conditions are maintained within the fractionator 2B so as to produce a vapor fraction of any desired end boiling point; for example, a fraction suitable for use in the preparation of aviation gasoline and comprising Preferably, the isobutane or other isoparamn is injected into the circulating stream of hydrocarbons and acid substantially in advance of the point of introduction of the fresh oleiin feed, and preferably on the suction side of the pump 8 so as to be thoroughly emulsified with the acid prior to contact with the olefin stock. In this way the presence of excess isoparaflin in the circulating stream may be assured prior to and during the time that the olefin hydrocarbons come into contact with the acid. Thus, polymerization of the olefin hydrocarbons by the acid is minimized, such that catalyst deterioration is eilectively retarded; and oleiin polymers which may be formed are alkylated to saturated motor fuel hydrocarbons.

The proportion of reaction mixture from reactor 4 which is recirculated varies between aboutl 10-parts to 25 parts by volume to one part of reaction mixture which is passed to settler 6. The amount of isobutane in the acid-isobutane mixture in the closed circuit can vary from about 3 to '7 parts, or higher by volume, for one part of olen charged. The acid in the agitated portion of the system exclusive of the settler is preferably maintained from about 0.5 to 2 parts to one part of total hydrocarbon by volume.

Any desired proportion of the used catalyst Withdrawn from the bottom of the settler 6 may be passed through a pipe 32 and thus recycled to the reactor That portion not recycled may be drawn oi from the system as indicated.

The cooling coil 2 serves to cool the circulating mixture and assist in maintaining the desired temperature by dissipating a portion of the heat of reaction. Also, as a result of passage through the cooling coil thorough agitation is brought4 about so that intimate mixing between the hydrocarbons and the acid is realized prior to introduction to the reactor 4.

While a single 4reaction stage has been described, it is intended that a plurality cf such reaction stages may be employed, if desired. Either concurrent or countercurrent ow of catalyst and hydrocarbons through the successive stages may be employed while retaining the principle of internal recycling in each stage, as has been described above. In a multistage unit, each an end boiling point of about 311 F. This fraction is drawn oil'as a vapor through a pipe 21 and condensed in a condenser 28. The higher boiling constituents accumulating in the bottom of the fractionator 28 are drawn off through a pipe 29.

The fresh sulphuric acid catalyst is kdrawn from a source not shown through a pipe 30 and injected into the suction side of the circulating pump 9.

Sufficient make-up isobutane, over that introduced with the charge through pipe I and the the pipe 22, is drawn from a source not shown and passed through a pipe 3l communicating with pipe 23 and through which the added isoparamn is introduced to the system to maintain the desired high iSObutane fr0 olen ratio.

stage may be provided with a settler, or there may be only a nal settler for the last stage.

Where the catalyst comprises sulphuric acid, it is usually preferable to use an acid having a concentration of about 96 to 100% H2SO4. The amount of fresh acid added through the pipe 3l) may be about 1/5 to t@ or less of the volume of the total liquid alkylate produced.

The temperature of reaction ranges from around 30 to 100 F. and, preferably, about 60 to 90 F., for H2SO4; and about '10 F. to 130 F. and, preferably, about 90 F. to 120 F., for the BFgJ-IzO complex.

The pressure in the alkylation vreactor and in the recirculating line may vary from approximately atmospheric up to the normal pressures used for C4 or C3 and C4 alkylation, such as about r 30 to 100 poundsv per square inch gauge.

f commercial cracking operations.

l thereof, and therefore only such limitations should -be imposed as are indicated in the appended claims.

I claim:

1. In a process for alkylating isoparafiin hydrocarbons with olefin hydrocarbons in the presence of a uid alkylation catalyst, the method comprising maintaining in a reaction vessel a mixalkylating conditions such that isoparaflins are reacted with olefins and alkylated hydrocarbons are formed, continuously withdrawing from the vessel a quantity of reaction mixture and subsequently returning it to the vessel together with a substantial quantity of catalyst, in a confined lture of said hydrocarbons and catalyst under stream, injecting in said stream prior to return to the vessel the fresh olen and paraiin hydrocarbon feed, injecting excess isoparaiiin hydrocarbon into said stream prior to introducing the fresh olefin hydrocarbons, withdrawing another portion .of' reaction mixture from the reaction vessel, and separating alkylated hydrocarbons from the portion so Withdrawn.

2. The method according to claim 1 in which the fluid alkylation catalyst comprises concentrated sulphuric acid.

' 3. In a process for the alkylation of isoparaflin hydrocarbons in the presence of a fluid alkylation catalyst, the method comprising the steps of maintaining a circulating liquid emulsion stream comprising catalyst and isoparafiin in a substantially closed circuit, said circuit comprising in part a restricted zone of fluid flow ln a confined stream and in part an enlargedzone, introducing to said restricted zone additional isoparain hydrocarbons so as to maintain a substantial excess over that required for reaction with .the olefins to be treated, introducing the olefins ingas phase to said stream at a location in the direction of liow of said stream beyond the locus of introduction of said additional isoparaiiin such that the additional isoparafin becomes emulsifled with said stream prior to the contact of the said feed olefins therewith, whereby the gaseous feed olefins are absorbed in said fiowing stream in the presence of the emulsied excess isoparaiiin, the said mixture then lowingto said enlarged zone under conditions such that alkylation of isopara-illn with the oleiins occurs, and continuously withdrawing a portion of the circulating stream and separating alkylate therefrom.

4. The process according to claim 3 in which the .catalyst comprises concentrated sulphuric acid.

5. In a continuous process for alkylating isoparaflin hydrocarbons Withv Aolefin hydrocarbons in the presence of a fluid alkylation catalyst, the steps comprising maintaining a substantial body of catalyst and hydrocarbons undergoing treatment in a reaction stage, contini' ously withdrawing reaction mixture froml said stage, separately removing alkylated hydrocarbons and catalyst;l

from a portion of the withdrawn mixture, discharging the removed catalyst and alkylated hydrocarbons, and recycling another portion of the withdrawn mixture to the reaction stage, subjecting the recycled catalyst and hydrocarbons to turbulent flow in a confined stream prior to return to the reaction stage, introducing additional isoparafiin hydrocarbon into said confined stream to maintain the lsoparaliin content thereof sub-- stantially in excess of that required for reaction with the olefins, and introducing the feed olen to said confined stream at a location in the direction of flow of said stream subsequent to the locus of addition of the added isoparaflin such that the added isoparaflin is emulsied with the said stream prior to contact with the said feed olefin. y

6. The process according to claim 5 in which the catalyst comprises concentrated sulphuric acid.

7 In a process for the alkylation of isoparaiiin hydrocarbons in the presence of a fluid alkylation catalyst, the method comprising the steps of maintaining a circulating liquid emulsion stream comprising catalyst and isopara-iiin in a substantially closed circuit, said circuit comprising in part a restricted zone of fiuid fiow in a confined stream and in part an enlarged zone, introducing to said restricted zone additional isoparain so as to maintain a substantial excess over that required for reaction with the olefin to be treated, introducing a hydrocarbon feed including olefin and paraiiin hydrocarbons in gas phase to said stream whereby the gaseous feed olefin is absorbed in said stream while in the presence of excess isoparailin including the added isoparafn, the said mixture then passing to said enlarged zone under conditions such that isoparafiin is alkylated with the olefin, releasing unabsorbed gases from said enlarged zone, withdrawing a portion of the reaction mixture from said circulating stream, separately removing alkylated hydrocarbons and catalyst from the Withdrawn reaction mixture and recycling at least a f part of the removed catalyst to the circulating stream. y

8. In a process for the continuous alkylation of an isoparaflin in the presence of a liquid alkylation catalyst, to produce gasoline hydrocarbons of high antiknock value, wherein a circulating liquid emulsion stream comprising catalyst and isoparafiin is maintained in a substantially closed circuit comprising a restricted zone of fluid fiow in a confined stream and an enlarged zone, fresh feed comprising isoparafiin and olenic reactants are continuously introduced into said circulating stream with the isoparaflin maintained in substantial molar excess of the equivalent olen content under conditions whereby the isoparaflin is alkylated with the olenic reaetant to form reaction products comprising gasoline hydrocarbons of high anti-knock value, and a portion of the reaction products are continuously removed from said circulating stream to a settling zone where hydrocarbons are separated from catalyst, the improvement which comprises introducing feed isoparaiiin into the restricted gone of said circulating liquid emulsion stream at a point substantially in advance of the introduction of the olelinic reactant into the said restricted zone in the direction of flow of said circulating stream,

whereby the feed isoparaflin is emulsifled with the -catalyst prior to contact with the oleiinic reactant.

9. The method according to claim 8, wherein at least a portion of the catalyst separated from the hydrocarbons in the said settling zone is recycled to the saidcimuting stream. and the reed isoparain is introduced into the said catalyst recycle stream and the mixture then introduced into the said circulating emulsion stream.

1o. The method according to cnam s,Y wherein y hydrocarbons separated from catalyst in said settlingzone are fractionated to separate gasoline hydrocarbons from unreacted excess isoparaln, and at least a portion of the said excess isoparamn is recycled to the said circulating claim 8, wherein y hydrocarbons from unreacted excess isoparaiiln,

at least a portion of the said excess isoparain is recycled to the said circulating stream, at least a portion of the catalyst separated in said settling zone is also recycled to the said circulating stream, and the recycle isoparain, fresh feed isoparaiiln and recycle catalyst are mixed and then introduced into and emulsied with said circulating stream prior to the contact of said feed oleilnic reactant therewith.

12. The method according to claim 8, wherein hydrocarbons separated from catalyst in said settling zone are fractionated to separate gasoline hydrocarbons from unreacted excess isopara-ln, at least a portion of said excess isoparailln is recycled to the said circulating stream, a portion of the catalyst separated in said settling zone is also recycled to the said circulating stream, another portion ofthe catalyst is discharged, fresh acid is introduced to make up for that discharged, and the said recycle isoparaln, fresh feed isoparafiin, recycle acid and fresh feed acid are all introduced into said circulating stream and emulsiiled therewith prior to the contact of said feed olenic reactant therewith.

13. In a process for the continuous alkylation of an isoparailin in the presence of a liquid alkylation catalyst, wherein feed isoparafn and olenic reactants are continuously introduced into` a recirculating emulsion stream of catalyst and hydrocarbon, the mixture agitated under conditions such that alkylationof isoparaihn with the oleiln reactant occurs, a portion of said reaction products is continuously withdrawn from said recirculating stream to a settling zone where hydrocarbons are separated from catalys hydrocarbons are fractionated to separate alkylate and unreacted isoparadiln, and at least a portion of the separated catalyst andv unreacted isoparaftln are continuously recycled to said recirculating emul- 'the improvement which comprises thoroughly emulsifying the feed isoparafn and the recycled isoparafdn with said catalyst recycle stream prior to the contact oi the said oleilnie reactant therewith.

i4. The method according to sion stream,

claim 13 wherein the catalyst is sulfuric-acid of alkylatlon strength.

15. In a process for the continuous alkylation of an isoparailln in the presencevof aliquid alkylation catalyst to produce gasoline hydrocarbons or high anti-knock value, wherein a cir-I culating liquid emulsion stream comprising catalyst and isoparamn is maintained in a substantially closed circ t comprising a restricted zone ofiiuid flow in a'coniined stream and an tains both normally `zone with a circulating pump positioned within said restricted zone. feed hydrocarbons including isoparailln and olen are continuously introduced into said circulating stream, and agitated therein under conditions whereby isoparamn is alkylated with the olen to produce of high anti-knock value, and a portion of the circulating stream is continuously withdrawn to a settling zo e where hydrocarbons are settledl from catalyst, the improvement which comprises introducing the feed olefin in gas phase into said restricted zone at a point adjacent the suctiony side of said pump, whereby the olen is absorbed in the circulating stream in the presence of the isoparaiiin. and feed isoparailln is introduced into said restricted zonaat a locus sufilciently in advance of said pump in the direction of iiow of said stream whereby the feed isoparafiin is emulsied with the catalyst stream prior to contact of the feed oleiln therewith.

16. 'I'he method according to claim 15, in which the oleiin is fed into the circulating stream in a hydrocarbon mixture comprising normally gaseous olen and parafiln hydrocarbons in the gas phase, and unabsorbed gases resulting from the Vsaid mixture in the circulating stream are removed from the latter when the stream reaches said enlarged zone.

1 7. The method according to claim 15, wherein at least a portion of the catalyst separated in said settlingk zone is recycled to the circulating stream, and feed isoparanin is mixed with the recycle catalyst prior to the introduction of the latter into said circulating stream.

18. In the continuous alkylation of an isoparamn with a normally gaseous olefin in the presence of a liquid alkylation catalyst capable of absorbing said olenn and normally tending to cause polymerization thereof, the improvement which comprises owing a feed mixture oi.' the said liquid catalyst and the said isoparaiiln in liquid phase and free from olefin through a restricted zone of suilicient extent tocause thorough emulsiiication of the isoparafiinI with the liquid catalyst, there being a substantial excess of isoparaflin in the flowing emulsion stream over that required for reaction with olefin subsequently added thereto as hereinafter set forth, then in Jecting in gas phase a hydrocarbon stream containing the normally gaseous olen into the thoroughly emulsied isoparaflin-catalyst liquid stream, the gaseous olefin being absorbed in the liquid catalyst in the presence o1' the emulsiiied excess Aoi? liquefied isoparailin to minimize polyunder alkylating conditions. whereby isoparaiiin is alkylated with absorbed olefin in the presence of thesaid liquid alkylatlon catalyst, separating.` from the resulting reaction productsalkylate, ex-f cess isoparaiiln and catalyst and returning at -least a portion of both the separated excess isoparailin and catalyst to the first-mentioned restricted zone .for re-emulsiilcation and reuse in the process.

19. The method according to claim 18, wherein I the said hydrocarbon stream in gas phase congaseousl oleiin. and paraffin hydrocarbons, and unabsorbed parailin gases are released from thefiowing emulsion stream in said amlation reaction zone.,

enlarged taining catalyst il withdrawn 20.' The method according to claim 18, wherein a portion of the mixed reaction products congasoline hydrocarbons from said reaction zone and recycled to said restricted zone to form a part of the owing emulsion stream.

21. In a process for the continuous alkylation of an isoparan in the presence of a liquid alkyls.- tion catalyst, wherein a recirculating emulsion stream of isoparamn and liquid alkylation catalyst is established and maintained in a closed circuit, feed Visoparaflin and olen reactant are added thereto and the mixture agitated under conditions such that alkylation of isoparaflln with 10 the olen reactant occurs, a portion of said reaction products is continuously withdrawn from said recirculating stream to a. settling zone where hydrocarbons are separated from the catalyst,

and catalyst is added to said recirculating stream 15 ARTHUR R. GOLDSBY. 

